Compounds with multiple acrylic radicals, compositions containing them, and uses thereof

ABSTRACT

Compounds with multiple acrylic radicals, the average composition of which has the general formula:

The present invention is concerned with compounds with multiple acrylicradicals, with compositions containing the same and also with processesfor their preparation; it is also concerned with the use of thesecompounds and compositions.

The compounds with multiple acrylic radicals according to the presentinvention are mixtures, the average composition of which has the generalformula

X--Y-(Z)_(m) _(-p) _(-l) ]_(n) (I)

wherein X is the radical derived by removing the OH groups from the COOHgroups of an organic carboxylic acid containing n COOH groups and thenumber of carbon atoms of which is between 14 and 90 and preferablybetween 18 and 54.

Y is the radical derived by removing m-p hydrogen atoms from thehydroxyl groups of an organic compound containing m OH groups,

Z is the monovalent radical derived by removing the OH group from theCOOH group of an organic monocarboxylic acid containing at least oneterminal CH₂ =CH-COO- radical,

n is a whole number of from 1 to 6 and preferably of from 1 to 4,

m is a whole number of from 2 to 8 and preferably of from 3 to 6, and

p is a number of from 0 to 2.5

With the proviso that m-p-l is a positive number different from zero andthat n(m-p-l) is between 2 and 15.

It is essential that the organic carboxylic acid, the radical of whichis designated X in the above general formula, has the hydrophobiccharacter of a higher fatty acid; it is for the reason that it contains14 to 90 carbon atoms and preferably 18 to 54 carbon atoms. The organiccarboxylic acid radical may be saturated or unsaturated and straight orbranched; in addition, it contains from 1 to 6 and preferably from 1 to4 carboxyl groups. Instead of the free acid, it is also possible to usefunctional derivatives, such as acid halides, anhydrides, esters, saltsor the like. However, according to the invention, for certainapplications, it is also possible to replace up to 75 mole percent ofthe organic carboxylic acid containing at least 14 carbon atoms by oneor more mono- or polycarboxylic acids containing less than 14 carbonatoms, such as adipic acid, maleic anhydride, HET acid,tetrabromophthalic anhydride, isophthalic acid or the like.

Examples of monocarboxylic acids XOH (n = 1) which can be used in thecompounds of the present invention include the saturated and unsaturatedmonocarboxylic fatty acids containing at least 14 carbon atoms, such asmyristic acid, palmitic acid, stearic acid, arachidic acid, behenicacid, lignoceric acid, cerotic acid, montanic acid, oleic acid,ricinoleic acid, linoleic acid and linolenic acid; mixtures of fattyacids originating from vegetable fats, such as palm oil, linseed oil,dehydrated or non-dehydrated castor oil, perilla oil, soya oil,safflower oil, Chinese wood oil oiticica oil, cotton seed oil, tall oiland the like; mixtures of fatty acids originating from animal fats, suchas tallow, lard, whale oil, fish oils and the like; and saturated andunsaturated synthetic fatty acids having the number of carbon atomsindicated above.

Examples of dicarboxylic and polycarboxylic acids X(OH)_(n) (n = 2 to 6)which can be used in the compounds of the present invention are thedimerized and trimerized fatty acids derived from fatty acids containingtwo or three double bonds, such as the Empol commercial products of thefirm Emery Industries, Inc. and the Hystrene products of the firm HuncoChemical Products Ltd., the dimer of methyl linoleate, the chlorides ofthese dimers, lower dicarboxylic acids carrying a long chain hydrocarbonradical, for example dodecyl-, tetradecyl-, hexadecyl- and octadecyl-succinic acids and the like, and also the lower dicarboxylic acidscarrying a thiohydrocarbon radical, for example dodecylthiosuccinic acidand the like; the Diels-Alder addition products of maleic anhydride witha fatty acid or a drying oil containing conjugated double bonds, forexample conjugated linoleic acid, alpha or beta-eleostearic acid, Chinawool oil, oiticica oil and the like; the reaction products of maleicanhydride with fatty acids or oils containing one or more non-conjugateddouble bonds; the reaction products of polycarboxylic acids or theiranhydrides (maleic, succinic, phthalic, trimellitic, pyromellitic acidsand anhydrides and the like) with hydroxylated long chain compounds, forexample ricinoleic acid, higher fatty alcohols, epoxidized higher fattyacids, oils containing hydroxylated higher fatty acids, for examplecastor oil, or epoxidized natural oils; polycarboxylic acids preparedfrom an alkyd resin containing higher fatty acid radicals and an excessof di- or polycarboxylic acid, which consequently are alkyd resins incarboxyl groups, the alkyd resins rich in carboxyl groups obtained bycondensing a dimer or trimer acid containing at least 14 carbon atomsand a diacid having a chain which is shorter than 14 carbon atoms with apolyhydroxylated compound; the addition products of lower to highermono- or polycarboxylic mercapto acids with unsaturated fatty acids,oils or alkyd resins, such as the addition product of mercaptobutyricacid with linseed oil, the addition product of thioglycolic acid withlinolenic acid and the like; brassylic acid (High Polymers, vol.27,Wiley-Intersciences, p.88-91); the dicarboxylic acids having 19 carbonatoms obtained by the KOCH synthesis, the OXO synthesis of ROELEN andthe REPPE reaction (High Polymers, vol.27, Wiley-Intersciences,p.97-110); and the like.

The organic compound, the radical of which is designated Y in the abovegeneral formula contains from 2 to 8 and preferably from 3 to 6 hydroxylgroups in the molecule. It can be a diol, such as ethylene glycol,propylene glycol, 1,4-, 1,3-, or -2,3-butane-diol, 1,6-hexane-diol,neopentyl glycol, diethylene glycol, dipropylene glycol, dibutyleneglycol, the polyethylene glycols, the polypropylene glycols or the like.However, the hydroxylated compound preferably contains at least 3hydroxyl groups, examples of these including glycerol,trimethylolethane, trimethylolpropane, pentaerythritol,dipentaerythritol, tripentaerythritol, sorbitol, mannitol, inositol,pinitol, quebrachitol, alpha-methylglycoside and the like, as well asthe hydroxylated products obtained by the condensation of ethylene orpropylene oxide with aforesaid polyalcohols. It is also possible to usepolyhydroxylated polymers, such as polyether alcohols and polyesteralcohols as well as their oxyalkylation products with ethylene oxide orpropylene oxide.

The organic monocarboxylic acids containing at least one terminal CH₂=CH-COO- radical providing the monovalent radical Z include, forexample, acrylic acid, the reaction product of one mole of a saturatedor unsaturated dicarboxylic acid or anhydride with one mole of ahydroxyalkyl acrylate, for example the reaction product of2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, 4-hydroxybutylacrylate, 6-hydroxyhexyl acrylate, 8-hydroxy-octyl acrylate,10-hydroxydecyl acrylate, 12-hydroxydodecyl acrylate or the like withsuccinic anhydride, maleic anhydride, phthalic anhydride, adipic acid,sebacic acid, itaconic acid or the like; the reaction product of twomoles of a hydroxyalkyl acrylate with one mole of a triboxylic acid oranhydride, such as trimellitic anhydride, aconitic acid or citric acid;the reaction product of three moles of a hydroxyalkyl acrylate with onemole of a tetracarboxylic dianhydride or acid, such as pyromelliticanhydride or acid, or any other organic compound containing at the sametime at least one free carboxyl group (or the chemical equivalent of acarboxyl group, such as an acid halide, anhydride, ester, salt orsimilar group) and at least one terminal CH₂ =CH-COO- radical.

For the preparation of compounds with multiple acrylic radicalscorresponding to the above general formula, various processes areavailable.

One-stage process (Process No. 1)

Stoichiometric quantities of the constituents providing the radicals X,Y and Z in the above general formula (i.e. one mole of the higherorganic carboxylic acid X(OH)_(n), n moles of the organic compoundYH_(m) and n(m-1) moles of the monocarboxylic acid ZOH with at least oneterminal CH₂ =CH-COO- radical) are heated in an organic,water-entraining sovent (benzene, toluene or the like) in the presenceof a radical polymerization inhibitor (hydroquinone, cuprous oxide orthe like), an esterification catalyst (sulfuric acid, p-toluene-sulfonicacid or the like) and optionally an additive preventing the colorationof the products obtained (for example triphenyl phosphite or the like).The reaction can be carried out at atmosphere pressure, advantageouslyin an inert atmosphere (nitrogen or the like) at a temperature of about70°-140°C., for a period of 2 to 10 hours with removal of the water ofesterification with the aid of the solvent.

The reaction is stopped as soon as the desired degree of esterification(measured in accordance with the amount of water of esterificationcollected) has been reached.

After having eliminated in known manner the solvent, the catalyst,excess inhibitor and any excess of monocarboxylic acid ZOH containing atleast one terminal CH₂ =CH-COO- radical, a product of the presentinvention is obtained, which can be used, either untreated or after asuitable purification, for its various applications.

The reaction product thus obtained is a mixture of compounds having agiven molecular weight distribution, as can be shown by gel permeationchromatography, the average composition of which, however, has thegeneral formular I given above. The products of the invention have awell defined content of hydroxyl groups. In formula I, p represents theaverage number of free hydroxyl groups which remain unreacted in the endproduct after esterification.

This one stage process is preferred for reasons of simplicity ofoperation and economy. However, similar end products with an averagecomposition of the formula I given above can be obtained by one of thefollowing two-stage processes.

Two-stage processes (Processes Nos. 2a and 2b).

a. Under esterification conditions similar to those described for thesingle-stage process, the organic compound YH_(m) is first esterifiedwith the higher organic carboxylic acid X(OH)_(n), whereupon theresidual hydroxyl groups of the organic compound YH_(m) are esterifiedwith the monocarboxylic acid ZOH containing at least one terminal CH₂=CH-COO- radical.

b. Alternatively, the organic compound YH_(m) is first esterified withthe monocarboxylic acid ZOH, only one hydroxyl group preferably beingallowed to remain in the organic compound YH_(m), whereupon the latteris esterified with the higher organic carboxylic acid X(OH)_(n).

In the single-stage or two-stage processes described above, the freeacids X(OH)_(n) and ZOH may be replaced by the halides, preferablychlorides, or anhydrides of these acids. Particularly in the case ofacid halides, this makes it possible to carry out the esterification atmore moderate temperatures, for example below about 40°C.; in this case,it is advantageous to carry out the esterification in the presence of anacid acceptor, such as pyridine, triethylamine or the like.

In addition, the compounds of the present invention can also be obtainedby transesterification of the organic compound YH_(m) with lower alkylesters of the acids X(OH)_(n) and ZOH. In this case, thetransesterification is carried out in a solvent having a sufficientlyhigh boiling point (for example toluene or the like) to ensure that thereaction takes place at the boiling temperature of the mixture at anadequate speed and that an azeotropic mixture is formed with the loweralcohol freed by the transesterification. The rate oftransesterification is monitored by measuring the amount of loweralcohol thus liberated, which is collected.

In the Table I given below some non-limitative examples are given of thecompounds with multiple acrylic radicals according to the presentinvention. The Table shows the number of the compound with multipleacrylic radicals, the nature and the molar proportion of each of theconstituents X, Y and Z, together with the number of the preparationprocess (1 = single-stage process; 2a = two-stage process with reactionfirst between X(OH)_(n) and YH_(m) ; 2b = two-stage process withreaction first between YH_(m) and ZOH).

The abbreviations used in this Table have the following meanings:

Ada: adipic acid

MA: maleic anhydride

PA: phthalic anhydride

Hea: hydroxyethyl acrylate

HPA: 2-hydroxypropyl acrylate

(ADA + HEA): addition product of adipic acid and hydroxyethyl acrylate

(MA + HEA): addition product of maleic anhydride and hydroxyethylacrylate

(PA + HEA): addition product of phthalic anhydride and hydroxyethylacrylate

(MA + HEA): addition product of maleic anhydride and 2-hydroxypropylacrylate

dimer acid =

Empol (emery Industries Inc.) : the dicarboxylic dimerization productsof C₁₈ unsaturated monobasic fatty acids. The reaction of dimerizationmay however leave a certain percentage of unpolymerized monobasic acidand/or produce a certain percentage of trimer acid. According to thecomposition of the dimer obtained, several commercial products arecharacterized by a number following the Registered Trade Mark EMPOL.Thus

Empol 1010 is the purest commercial dibasic C₃₆ dimer, containing only3% trimer and no monobasic acid;

Empol 1022 is a dimer acid containing 19-22% trimer and 5% monobasicacid;

Empol 1038 is the same as the preceding one but less coloured. Dimeracid chloride : acid chloride of EMPOL

Pluracol sp 760: addition product of about 12 moles of ethylene oxide on1 mole of sorbitol, having a molecular weight of about 700

Pluracol peP 450: addition product of about 7 moles of ethylene oxide on1 mole of pentaerythritol having a molecular weight of about 400

Tercarol g 310 (glycerol + 3 moles propylene oxide, molecular weightabout 310)

tetracid: esterification product of one mole of pyromellitic acid with 4moles of ricinoleic acid.

triacid: addition product of 2 moles of thioglycolic acid on 1 mole oflinolenic acid.

                                      TABLE I                                     __________________________________________________________________________    Compound                                                                             Constituent X moles                                                                              Constituent Y                                                                             moles Constituent                                                                            moles                                                                              Process             No                   of X             of Y           of                       __________________________________________________________________________                                                         Z                        1     ricinoleic acid                                                                              1    trimethylopropane                                                                         1    acrylic acid                                                                            3    1                   2     stearic acid   1    sorbitol    1    (ADA + HEA)                                                                             5    1                   3     oleic acid     1    dipentaerythritol                                                                         1    (MA + HEA)                                                                              5    1                   4     linseed fatty acid                                                                           1    Pluracol SP 760                                                                           1    (PA + HEA)                                                                              5    1                   5     dimer acid (EMPOL 1010)                                                                      1    pentaerythritol                                                                           2    acrylic acid                                                                            6    1                   6     dimer acid (EMPOL 1010)                                                                      1    Tercarol G 310                                                                            2    acrylic acid                                                                            4    1                   7     (MA + linoleic acid-9,12)                                                                    1    ethylene glycol                                                                           3    (MA + HPA)                                                                              3    1                   8     tetracid       1    trimethylolpropane                                                                        4    acrylic acid                                                                            8    1                   9     dimer acid (EMPOL 1010)                                                                      1    glycerol + 12 moles                                                                       2    (MA + HEA)                                                                              4    1                                             ethylene oxide                                      10    dimer acid chloride                                                                          1    pentaerythritol                                                                           2    acryloyl chloride                                                                       6    1                   11    (MA + linoleic acid-9,12)                                                                    1    Tercarol G 310                                                                            3    acrylic anhydride                                                                       3    1                   12    methyl linoleate dimer                                                                       1    glycerol    2    ethyl acrylate                                                                          4    1                   13a = oleic acid     1    Pluracol SP 760                                                                           1                                       13b   13a            1    +                acrylic acid                                                                            5     2a                 14a   stearic acid   1    Pluracol PeP 450                                                                          1                                       14b   14a            1    +                (MA +HEA) 3     2a                 15a =                     sorbitol + 12 moles                                                           ethylene oxide                                                                            1    acrylic acid                                                                            5     2b                 15b   oleic acid     1    + 15a                                               16    triacid        1    polyethylene glycol                                                                       3    acrylic acid                                                                            3    1                   17a =                     pentaerythritol                                                                           2    acrylic acid                                                                            6     2b                 17b   dimer acid (EMPOL 1010)                                                                      1    + 17a                                               __________________________________________________________________________

Two remarks have to be made regarding the above Table:

1. The respective molar proportions of the constituents X, Y and Z usedfor the preparation of the compounds with multiple acrylic radicalsaccording to the present invention were established with due regard tothe number of carboxyl groups and hydroxyl groups present in these threeconstituents. Nevertheless, important deviations may be admitted inrespect of these proportions, while still obtaining products within thescope of the present invention.

2. The end products obtained from the same starting materials by thedifferent processes mentioned above present a different molecular weightdistribution as can be shown by gel permeation chromatography. Theproducts obtained by the two-stage processes present a broader molecularweight distribution than the products obtained by the one-stage process.

The compounds with multiple acrylic radicals according to the presentinvention are liquid to waxy substances, the viscosity of which atambient temperature is between a few poises and several hundred poises.They are colourless to dark brown compounds, depending upon the qualityof the raw materials and the operating conditions used in the course ofthe synthesis. They have a good solubility in aromatic solvents,ketones, esters and the like, as well as in mono- and polyfunctionalvinylic and acrylic monomers. Their vapour pressure at ambienttemperature is practically negligible. Their hydrophobic character ismore or less pronounced, depending upon the raw materials used for theirpreparation.

The present invention is also concerned with the reaction productsobtained by reacting the mixture of compounds with the averagecomposition of formula (I) given above, wherein p is more than zero,with aliphatic, cycloaliphatic, heterocyclic or aromatic mono- ordi-isocyanates. The properties of the urethane-modified products thusobtained differ from the non-modified starting products by a higherviscosity and a lower hydroxyl number. Photopolymerizable inks andoverprint varnishes formulated with these modified resins dry at higherrates than the corresponding unmodified products. Due to an improvementof the rheological properties and a better equilibration of thehydrophobic/hydrophylic balance in the molecule, ultraviolet dryingoffset formulations, comprising said urethane-modified products, have abetter printing behaviour on high speed printing presses. Mechanicalproperties and chemical resistance of the cured film are improved onusing the urethane-modified products.

As non-limiting examples of isocyanates, mention may be made of thefollowing monoisocyanates: methyl-isocyanate, ethyl-isocyanate,propyl-isocyanate, butyl-isocyanate, cyclohexyl-isocyanate andphenyl-isocyanate; the following diisocyanates:hexamethylene-diisocyanate, trimethylhexyl-diisocyanate, dimer fattyacid-diisocyanates such as DDI produced by General Mills Chemicals,isophorone-diisocyanate, dicyclohexylmethane-diisocyanate,toluylene-diisocyanate and diphenylmethane-4,4'-diisocyanate; andurethanized adducts obtained by reacting diisocyanates withmonoalcohols.

In a preferred embodiment for the preparation of these urethane-modifiedcompounds, from 2 to 20% by weight of mono- or diisocyanates areprogressively added to the compounds with the average composition offormula (I) given above, in the presence of known catalysts, such asdibutyl-tin dilaurate, triethylene diamine etc. The reaction is carriedout between 40° and 80°C., preferably between 55° and 70°C., optionallyin the presence of inert solvents. In order to allow a certain number ofunreacted hydroxyl groups to remain in the end product, the molar ratioof isocyanate to hydroxyl groups in the reacting products is chosenbelow unity. In order to lower the viscosity, it is possible, forexample, to reduce the molecular weight of the compounds of the presentinvention by partial transesterification, in known manner, with a mono-or polyalcohol, such as methanol, ethanol, ethylene glycol, hydroxyalkylacrylate or the like having a molecular weight below 200.

Because of the presence of a plurality of acrylic unsaturation groups intheir molecules, the compounds according to the present invention arereadily polymerizable and can form three-dimensional cross-linkedpolymers under the following conditions: by the action of heat at atemperature between 50° and 250°C, preferably between 50° and 150°C.,preferably in the absence of oxygen; by the addition of radicalinitiators which decompose at a higher temperature (for example above40°C.) or even at ambient temperature, provided that an accelerator isadded; by exposure to ionizing radiation of electromagnetic nature(gamma-rays or X-rays) or of corpuscular nature (accelerated electrons),even in the presence of air and without any additive being necessary; invisible and or ultra-violet light, provided that a photosensitizer orphotoinitiator is added.

The compounds with multiple acrylic radicals according to the presentinvention may, therefore, advantageously be used as film-forming bindersfor all applications where rapid polymerization is required; being usedeither singly or mixed with other materials, such as inertnoncopolymerizable polymers; reactive copolymerizable polymers;copolymerizable oligomers; inert plasticizers; inert organic solvents;copolymerizable olefinically-unsaturated monomer compounds and variousadjuvants.

As examples of inert polymers, mention may, in particular, be made ofthe following: polyolefins, polystyrene, polyalkyl acrylates, polyvinylchloride, polyvinyl acetate, polyethers, polyamides, saturatedpolyesters, alkyd resins, epoxy resins, urea-formaldehyde resins,arylsulfonamideformaldehyde resins, terpene-phenol resins, polyvinylalkylethers, chlorinated rubber, cellulose esters (acetopropionate,acetobutyrate or the like), copolymers of vinyl chloride with vinylacetate, maleic esters, vinylidene chloride, vinyl esters or the like.

As examples of reactive copolymerizable polymers, mention may be made ofthe unsaturated polyesters and unsaturated alkyd resins, the unsaturatedresins obtained by reacting an unsaturated hydroxylated compound (forexample allyl alcohol, hydroxyethyl acrylate or the like) with theaddition product of a polyisocyanate (for example tolylene diisocyanate,hexamethylene diisocyanate or the like) and a resin having free hydroxylgroups (for example a hydroxylated polyester, a hydroxyalkyl acrylatecopolymer, a hydroxylated polyether or the like), this addition productstill containing free NCO groups. As examples of other reactive resinswhich can be used according to the present invention, reference is, inparticular, made to the article by A. Vrancken, XIth Fatipec Congress,June 11-16, 1972, Florence, pages 19 to 41.

The copolymerizable oligomers which can be added to the polymerizablecompounds according to the present invention are principally used whenit is required to modify the viscosity, the flow limit or the tack, forthe purpose of adapting the resulting product to various applicationsand/or technical utilisations. They are especially used for lowering theviscosity of the product obtained. At the moment of polymerization,these oligomers copolymerize with the compounds according to the presentinvention and thus finally form part of the compositions thus obtained.Examples of copolymerizable oligomers include the di-, tri- andpolyacrylates of hydroxylated products obtained by condensing ethyleneoxide or propylene oxide with glycerol, trimethylolpropane,pentaerythritol, sorbitol or the like.

The inert plasticizers which can be added to the compounds with multipleacrylic radicals of the present invention can be esters of organic ormineral acids, such as o-, iso- or terephthalic acid, adipic acid,azelaic acid, sebacic acid, citric acid or phosphoric acid, with mono-polyhydroxylated aliphatic and aromatic hydroxylated compounds, such asbutanol, 2-ethylhexanol, phenol, cresol, diethylene glycol, triethyleneglycol, dipropylene glycol or the like. It is also possible to useepoxidized oils, chlorinated paraffins, chlorinated polyphenyls,chlorinated naphthalenes or the like as plasticizers.

If desired, it is possible to add inert organic solvents, such as ethylacetate, methyl ethyl ketone or the like, to the compounds with multipleacrylic radicals of the present invention, these solvents being mainlyadded in order to lower the viscosity. Nevertheless, it is preferablenot to use solvents because the problems of recovery, intoxication andpollution caused by solvents are thus eliminated. As mentioned above,according to the present invention, it is, in fact, possible for theviscosity of the compositions prepared from the compounds with multipleacrylic radicals of the present invention to be regulated at will, sothat the viscosity may vary from a few poises to several thousand poisesat 25°C., thus making the use of organic solvents unnecessary.

On the other hand, it may be advantageous for copolymerizableolefinically-unsaturated monomer compounds to be used with the compoundsof the present invention. Depending upon the intended use, thesemonomers may or may not be volatile and may contain one or moreolefinically-unsaturated bonds. Examples of these copolymerizableolefinically-unsaturated compounds include styrene, vinyl acetate, vinylchloride, vinylidene chloride, the mono-, di- and polyacrylates of di-,tri- and polyols, such as trimethylolpropane triacrylate,pentaerythritol tri- and tetraacrylate and the like. Like thecopolymerizable oligomers mentioned previously, the copolymerizableolefinically-unsaturated monomer compounds may be added to the compoundswith multiple acrylic radicals of the present invention in order tomodify their viscosity and in copolymerized form they will form part ofthe final polymer products thus obtained.

The following examples are given of adjuvants which can be added to thecompounds according to the present invention: known heat and lightstabilizers, known antioxidizing agents; known viscosity modifyingagents or thixotropic agents, known flow agents, chain transfer agentsserving to accelerate the radical polymerization once it has beenstarted (examples of these agents include di- and triamines,alkanolamines, monoalkyldialkanolamines and dialkylmonoalkanolamines,morpholine and its derivatives, polyamines, N-phenylglycine and itsderivatives, N,N'-dimethylmonoethanolamine monoacrylate,N-methyldiethanolamine diacrylate, triethanolamine triacrylate, and thelike); polymerization inhibitors intended to provide stability duringstorage (for example quinones, hydroquinones, substituted phenolderivatives, primary aromatic amines, copper compounds and the like);waxes, the purpose of which is to assist the obtaining of non-scratchinghardened films, which waxes may be natural, such as candelilla wax,Carnauba wax or the like, or synthetic, such as polyethylene,polypropylene or paraffin wax, chlorinated paraffins, chlorinatednaphthalenes or the like; pigments, dyes, mineral or organic fillers,fibrous or pulverulent reinforcing agents, and the like.

The compounds according to the present invention can be used for variouspurposes, some non-limitative examples of which are given below:

By the addition of radical initiators (peroxides, hydroperoxides,percarbonates, azo compounds or the like) decomposing under theinfluence of heat, the compounds of the present invention can be used ascasting, compression moulding, injection moulding and extrusion resins.Because of the excellent flexibility of the products obtained accordingto the present invention, they may be added to polyvinyl chlorideplastisols at the rate of 5-30% by weight of the total composition, asreactive plasticizers to assist adhesion to metal sheets and to increasethe cohesive force of the film applied.

By the addition of accelerators to some of the initiators describedabove, for example by adding dimethyl-p-toluidine to benzoyl peroxide,cobalt naphthenate to methyl ethyl ketone peroxide or the like, thepolymerization of the compositions according to the present inventioncan be initiated at ambient temperature. Compositions of theseformulations may be used, in particular, as road marking paints. In thisparticular case, paraffin is added to the formulations so that, afterapplication to the substrate, the paraffin separates out and forms asurface film providing protection against the action of atmosphericoxygen. Another typical application of the compositions according to thepresent invention is as anaerobic adhesives in which theinitiator-accelerator pair is appropriately selected. These compositionshave the property of not polymerizing in the presence of air, so thatthey can be stored for several months at ambient temperature. If,however, the presence of oxygen is excluded, these adhesives start topolymerize slowly. Furthermore, the presence of metallic ions, such asiron ions, has the effect of considerably increasing the speed ofpolymerization, so that they can be used for locking metallicconnections under anaerobic conditions.

In the complete absence of initiators, accelerators and the like, thecompositions according to the present invention can be polymerizedextremely rapidly by accelerated electron beam curing. They can,therefore, be used for the production of varnishes, paints, coatings orthe like and serve for the industrial coating of a large variety ofsubstrates, including particule wood boards, chip boards, fibre boards,hardboard, paper, metal, asbestos-cement and the like.

If photosensitizers and/or photoinitiators are added to the compositionsof the present invention, compositions are obtained which can bepolymerized under the influence of light having one or more wavelengthsbetween 200 nm and 5000 nm. The photosensitizers supply to all themolecules containing one or more unsaturations or to the initiator, partof the energy transmitted by the light. By means of the unsaturatedsystem or systems or of a photoinitiator, the photosensitizers producefree radicals or ions which initiate the polymerization or thecross-linking of the composition.

With regard to the photosensitizers or photoinitiators which can be usedaccording to the present invention, the following references are inparticular quoted: G. Delzenne, Ind.Chim.Belge, 24, 739-764/1959; J.Kosar, "Light Sensitive Systems", pub. Wiley, New York, 1965; N. J.Turro, "Molecular Photochemistry", pub. Benjamin Inc., New York, 1967;H. G. Heine et al., Angew.Chem.84, 1032/1972.

The photoinitiators are essentially chemical substances belonging to oneof the following major categories: compounds containing carbonyl groups,such as pentanedione, benzil, piperonal, benzoin and its halogenatedderivatives, benzoin ethers, anthraquinone and its derivatives,p,p'-dimethylaminobenzophene, benzophenone and the like; compoundscontaining sulfur or selenium, such as the di- and polysulfides,xanthogenates, mercaptans, dithiocarbamates, thioketones,beta-napthoselenazolines; peroxides; compounds containing nitrogen, suchas azonitriles, diazo compounds, diazides, acridine derivatives,phenazine, quinoxaline, quinazoline and oxime esters, for example1-phenyl-1,2-propanedione 2-[0-(benzoyl)oxime]; halogenated compounds,such as halogenated ketones or aldehydes, methylaryl halides, sulfonylhalides or dihalides; and photoinitiator dyestuffs, such as diazoniumsalts, azoxybenzenes and derivatives, rhodamines, eosines,fluoresceines, acriflavine or the like.

The photosensitizers belong to one of the following categories: ketonesand their derivatives, carbocyanines and methines, polycyclic aromatichydrocarbons, such as anthracene or the like, and dyestuffs, such asxanthenes, safranines and acridines.

After the addition of 0.1 to 10% by weight of photoinitiators and/orphotosensitizers, the products of the present invention or mixturescontaining these products can be used for the production of transparentvarnishes for coating a large variety of substrates, for example thosewhich have been mentioned above for the polymerization by acceleratedelectron beams.

They can also be used for the production of semi-transparent sealershaving a high content of transparent fillers and coloured sealerscontaining dyestuffs which are transparent to part of the emissionspectrum of the lamp. The fillers are selected so as to have a minimumabsorption at the wavelengths of from 200 to 700 nanometers of thespectrum. They include, in particular, precipitated or micronizedcalcium or magnesium carbonate (calcite, aragonite or the like), bariumor calcium sulfate (baryta, blanc fixe or the like), micronized hydratedpotassium or magnesium silicoaluminate, micronized magnesium silicate,precipitated hydrated alumina, asbestine, micronized or non-micronizedtalc and the like.

The photopolymerizable compositions of the present invention can also beused as laminating or composite bonding glues for bonding safetyglasses, laminated packing films or composites, provided that at leastone element of the bonded material is transparent to ultra-violetradiation.

They can also be used in printed circuits, relief and gravure printingplates, photoreproduction, photoresists and the like.

A particularly advantageous field of use for the compounds of thepresent invention is for solventless ultra-violet inks, i.e. inks whichdry and harden under the action of ultra-violet rays. In this particularcase, very thin pigmented or coloured coats of these inks are applied,which, because of the low thickness applied, allow penetration ofultra-violet radiation to a sufficient depth to initiatephotopolymerization at a very high initiation speed.

Solventless inks are of interest in connection with the fight againstpollution. Conventional printing inks contain up to 45% of hydrocarbonswhich are eliminated in ovens. The solvents are discharged to theatmosphere, together with the combustion gases. This can be avoided bythe expensive installation of catalytic or thermal postcombustiondevices. However, in the case of accidental stoppage of the press, thepaper in the ovens might ignite, thus giving rise to a risk of fire andconsiderable expense for re-starting.

The use of ultra-violet inks reduces the overcrowding of a workshopequipped with sheet-fed presses. Dried ultra-violet inks have greatermechanical strength and chemical resistance, while the speed of dryingis considerably increased, thus leading to a reduction of waiting beforefinishing off, with a reduction of stocks of printed material in thecourse of production and the elimination of the use of anti setoffpowders, which give rise to premature wear of certain parts of the pressand entail difficulties in subsequent finishing, for example filmlamination.

The drying of inks, varnishes or lamination bonding products byultra-violet irradiation is a known technique which has been describedin numerous patents. Nevertheless, the quality of products available onthe market has retarded their adoption by the graphic arts industry. Inparticular, some known ultra-violet inks have insufficient storagestability or unsatisfactory drying properties, while others have gooddrying properties but, to a still greater extent than the first inksmentioned, entail considerable difficulties in obtaining the water/inkbalance in the offset process, which difficulties may even entailscumming or pronounced tinting. Furthermore, reproducibility withvarious manufacturing batches must be considered as inadequate becauseof the absence of definitions of chemical and physical characteristics(or control standards) which must be respected by the unsaturatedprepolymers and unsaturated monomers and/or oligomers used in thecomposition of these inks.

The products of the present invention are prefectly suitable for theproduction of offset, letterpress and flexographic inks and also forinks used for copperplate printing, gravure and silk screen printing,which dry under ultra-violet radiation.

The composition of inks and varnishes, which are photopolymerizable byultra-violet rays (abbreviated as UV inks) of the present invention canbe as follows:photopolymerizable binder 10-90% by weightinert polymersand plasticizers 0-40% by weightpigments and fillers 0-60% byweightphotoinitiators and/or photosensitizers which are activeat thewavelengths of 100 to 400 nanometers 1-15% by weightconventionaladditives for UV inks 1-10% by weight.

The polymerizable binder for the ultra-violet inks and varnishesaccording to the present invention comprises 5 to 100% by weight of atleast one compound with multiple acrylic radicals of the presentinvention and 0 to 95% by weight of at least one compound selected fromthe group consisting of (a) copolymerizable reactive unsaturatedpolymers, (b) copolymerizable unsaturated oligomers, and (c)copolymerizable unsaturated monomers, examples of constituents (a), (b)and (c) having already been given in the above description.

In order to obtain quickly drying UV inks, the compounds with multipleacrylic radicals of the present invention should average 2 to 15,preferably 4 to 9 CH₂ = CH-COO- groups per molecule.

Among these compounds (a), (b), (c), the compounds selected will bethose which have a good compatibility with the compounds with multipleacrylic radicals of the present invention and a comparable level ofpolymerization reactivity. These compounds are generally used formodifying the rheology of the inks or for improving adherence, forexample in the case of printing on tin plate, on aluminium, on sheets ofplastics material or the like. Compounds (b) and (c) are used mainly forthe purpose of lowering the viscosity of inks. The monomers (c) arepreferably selected from compounds having negligible volatility at 25°C.and a high acrylic radical content, for example trimethylolethanetriacrylate, trimethylolpropane triacrylate, glycerol triacrylate,butane-1,2,4-triol triacrylate, pentaerythritol tri- or tetraacrylate,dipentaerythritol tetra-, penta- or hexaacrylate or the like.

The inert polymers and plasticizers of the ultra-violet inks accordingto the present invention are selected from the products which havealready been mentioned above in the description, care being taken toensure good compatibility with the photopolymerizable binder and theother constituents of the ink, the absence of chemical interaction withthe other constituents of the ink and low absorption in the ultra-violetspectrum. The inert polymers are added to adapt or modify theprintability characteristics, the final appearance (gloss) and theproperties of the ink films obtained. The plasticizers are used, inparticular, in order to solubilize the photoinitiator and/or thephotosensitizer or other adjuvants.

The pigments and fillers for the ultra-violet inks according to thepresent invention are added in order to impart colorimetric properties.An ink or a varnish may contain 0 to 30%, preferably between 0 and 18%,of organic pigments which are transparent and semi-transparent toultra-violet rays, 0 to 60% of hiding mineral pigments, and 0 to 50% offillers transparent to ultra-violet rays, the total amount of fillersand pigments being between 10 and 60% in the case of ultra-violet inksand 0% in the case of overprinting. These pigments and fillers mustneither retard nor inhibit the photopolymerization of thephotopolymerizable binder. They must neither react chemically with thephotoinitiator or photoinitiators and/or photosensitizer orphotosensitizers, nor may they adsorb them physically.

The organic pigments can be selected from those products listed in theColour Index, the absorption of which at wavelengths of 200 to 500nanometers is as low as possible.

The utilization of opacifying or hiding mineral pigments may becomenecessary for the production of white inks, which is the case, forexample, with offset inks intended for printing on tin plate. Asexamples of opacifying pigments, there may be mentioned titanium, zinc,iron or chromium oxides, zinc or cadmium sulfides; manganese or ammoniumphosphates; cobalt aluminates or the like. It is obvious that theabsorption of ultra-violet rays by these opacifying pigments is higherthan with organic pigments which are transparent to ultra-violet raysand that inks formulated with these opacifying pigments necessitatehigher irradiation energy (expressed in milliwatts per square centimeterof printed surface). In other words, in order to obtain the same dryingrate, the number of ultra-violet radiators must be increased.

The fillers which are transparent to ultra-violet rays and intended forthe inks according to the present invention, which have already beenmentioned above in the description relating to sealers, may be added inorder to modify the rheological behaviour of the ink.

The photoinitiators and photosensitizers and also the various additivessuitable for ultraviolet inks have already been mentioned above in thedescription.

The compounds according to the present invention are characterized by abalance of the lipophilic and hydrophilic parts of the molecule whichmakes them particularly suitable for use for the formulation ofultra-violet offset inks. Unlike the binding agents used at the presenttime in ultra-violet offset inks, the balance between ink and dampeningsolution can easily be achieved and maintained on the press, even aftera halt in the printing, when the compounds according to the presentinvention are used. Isopropanol contents of the order of 15-20% may beused, without difficulty, in continuous dampening systems. Of thecompounds of the present invention, the best offset behaviour isobtained with those with a hydroxyl number between 10 and 80 andpreferably between 20 and 65, and with an acid number between 2 and 25and preferably between 5 and 15. The products of the present inventionhave the particular advantage of exhibiting complete inertia towards theink distribution rollers and towards the blankets which transfer the inkfrom the plate cylinders to the printing substrate.

The compounds of the present invention should have a viscosity between 2and 250 poises and preferably between 30 and 200 poises in the case ofinks intended for rotary offset and letterpress presses, and a viscositybetween 50 and 400 poises and preferably between 130 and 200 poises forsheet-fed offset or letterpress printing inks. The compounds of thepresent invention, the viscosity of which is lower than 30 poises,optionally mixed with photocopolymerizable monomers and/or oligomers,can be used for the formulation of flexographic, silk screen, andgravure inks.

The following Examples are given for the purpose of illustrating thepresent invention. All parts are by weight unless otherwise stated.

EXAMPLE 1.

A fraction of the hydroxyl groups of a polyol containing 6 hydroxylgroups per molecule (Pluracol SP760) is first esterified with a fattymonoacid in a double-walled glass reactor with a capacity of 3 litersand equipped with an agitator, a thermometer and an azeotropicdistillation column. For this purpose, the following amounts ofreactants are introduced into the reactor:

680 g. of sorbitol- 12 moles ethylene oxide addition product (PluracolSP760),

423 g. oleic acid,

300 g. benzene,

40 g. p-toluene-sulfonic acid,

1 g. cuprous oxide.

The mixture is brought to the boil under atmospheric pressure. When 27ml. of water of esterification have been collected in the course of theazeotropic distillation of the mixture, the latter is cooled to atemperature below 50°C. and the following are added:

480 g. acrylic acid

130 g. benzene

1 g. cuprous oxide

The mixture is again brought to the boil and the esterificationcontinued until no further water passes over by azeotropic distillation.

The mixture is cooled and 5 liters of benzene are added, whereupon it iswashed in succession with aqueous solutions of sodium chloride andsodium bicarbonate until neutral. 500 ppm hydroquinone are added and theunsaturated ester is isolated by distilling off the solvent in vacuo.

The final product has the following characteristics:

Viscosity: 2.5 poises at 25°C.

Oh value: 29

Acid value: 11

Acrylic unsaturation: 3.1 meq./g. (meq. = milliequivalent of acrylicacid)

Coloration: yellow

The viscosity was measured with the Hoppler viscosimeter. The acrylicunsaturation was calculated from the intensity of the band at 804 cm⁻ ¹of the infra-red absorption spectrum, measured in a solution of theproduct examined in carbon disulfide.

EXAMPLE 2.

The procedure of Example 1 was repeated but the oleic acid was replacedby 220 g. of an addition product of maleic anhydride and oleic acid.This product was obtained by reacting a mixture of 1.2 moles of maleicanhydride with 1 mole of oleic acid at 200°C. for 6 hours in a glassvessel, at atmospheric pressure. Part of the excess of maleic anhydridesublimates during the reaction, the remainder being evaporated at theend thereof. This addition product has an acid number of 385 and has anaverage maleic anhydride content of 0.7 mole per mole of oleic acid.

The final product, obtained under the experimental conditions of Example1, has the following characteristics:

Viscosity: 55 poises at 25°C.

Oh value: 27

Acid value: 15

Acrylic unsaturation: 4.3 meq./g.

EXAMPLE 3.

The procedure of Example 1 was repeated but the oleic acid was replacedby 750 g. of an addition product of maleic anhydride and linseed oil.This addition product was obtained by heating 1800 g. of linseed oil(iodine number = 190) and 200 g. of maleic anhydride at 250°C. for 4hours in an autoclave. The iodine number is then 135, the acid number is110 and the coloration of the product obtained is yellow. The additionproduct averages 1 mole maleic anhydride per mole of linseed oil.

The final product, obtained under the experimental conditions of Example1, has the following characteristics:

Viscosity: 72 poises at 25°C.

Oh value: 19

Acid value: 7

Acrylic unsaturation: 2.2 meq./g.

EXAMPLE 4.

The oleic acid of Example 1 is replaced by 190 g. of an addition productof maleic anhydride and beta-eleostearic acid. This latter product isobtained by a Diels-Alder reaction according to the process of R. S.Morrell and H. Samuels (J. Chem. Soc. 1932, 2251--54). The reaction isexothermic and takes place readily at 85°-90°C. The product contains onemolecule of maleic anhydride per molecule of beta-eleostearic acid andit is in the form of a yellowish-white solid having a melting point of77°C.

The final product, obtained under the experimental conditions of Example1, has the following characteristics:

Viscosity: 85 poises at 25°C.

Oh value: 25

Acid value: 14

Acrylic unsaturation: 4.7 meq./g.

EXAMPLE 5.

565 g. dimer acid containing 19-22% trimer and 5% monobasicunpolymerized acid (EMPOL 1022 of Emery Industries Inc., see descriptionabove)

272 g. pentaerythritol

576 g. acrylic acid

400 g. benzene

20 g. sulfuric acid (d = 1.84)

1 g. cuprous oxide

are introduced into a double-walled glass reactor with a capacity of 3liters and provided with an agitator, a thermometer and an azeotropicdistillation column.

The mixture is brought to the boil at atmospheric pressure. The water ofesterification resulting from the azeotropic distillation is collectedand the benzene is returned to the reactor. Esterification is completewithin 7 hours and 144 ml. of water are thus collected; in the course ofthis period, the boiling temperature of the contents of the flask risesfrom 92° to 105°C.

This mixture is diluted with 5 liters of benzene and washed insuccession with aqueous solutions of sodium chloride and sodiumhydrogen-carbonate until neutral. 500 ppm of hydroquinone are then addedand the unsaturated ester is isolated by driving off the solvent bydistillation in vacuo. Weight obtained: 1280 g., i.e. about 70% oftheory.

This ester, of dark brown colour, has the following characteristics:

Viscosity: 600 poises at 25°C.

Oh value: 25

acid value: 6

Acrylic unsaturation: 5.5 meq./g.

less than 0.1% by weight of residual benzene.

EXAMPLE 6.

By the procedure of Example 5, an unsaturated ester is prepared from thefollowing constituents:

565 g. dimer acid, same as the one used in Example 5 but less coloured(EMPOL 1038 of Emery Industries Inc., see description above)

408 g. pentaerythritol

720 g. acrylic acid

500 g. benzene

34 g. p-toluene-sulfonic acid

2 g. cuprous oxide

There are thus obtained 1740 g. (about 80% of theory) of unsaturatedresin which is in the form of a viscous liquid (230 poises at 25°C.),the colour of which is brownish-yellow and which has the followingcharacteristics:

Oh value: 30

Acid value: 2

Acrylic unsaturation: 6.5 meq./g.

less than 0.1% of residual benzene.

EXAMPLE 7.

By the procedure of Example 5, an unsaturated ester is prepared from thefollowing components:

565 g. C₃₆ dimer acid containing only 3% trimer (EMPOL 1010 of EmeryIndustries Inc., see description above)

1360 g. of the 1 mole sorbitol- 12 moles ethylene oxide addition product(PLURACOL SP760)

864 g. acrylic acid

500 g. benzene

40 g. p-toluene-sulfonic acid

2 g. cuprous oxide.

The esterification takes 10 hours. The resulting unsaturated resin (1750g.) has the following characteristics:

Coloration: yellow

Viscosity: 50 poises at 25°C.

Oh value: 494

Acid value: 4

Acrylic unsaturation: 4.0 meq./g.

EXAMPLE 8.

In the reactor described in Example 5, pentaerythritol triacrylate isfirst prepared from the following constituents:

544 g. pentaerythritol

1152 g. acrylic acid

440 g. benzene

40 g. p-toluene-sulfonic acid

2 g. cuprous oxide

After 4 hours, the esterification is stopped and the excess of acrylicacid and the benzene are removed from the reaction mixture by passingtwice in succession through a thin layer evaporator.

The free hydroxyl group, which still remains in the reaction productobtained in this manner, is reacted with a dimer acid, this operationtaking place in the same reactor as was used for the partialesterification. The following are used for this purpose:

660 g. of the crude hydroxylated intermediate product

300 g. dimer acid (EMPOL 1010, see Example 7)

600 g. benzene

1 g. cuprous oxide

The esterification is continued for 5 to 6 hours under reflux, whereuponthe unsaturated resin obtained in this manner is purified and isolatedby the method described in Example 5.

The unsaturated resin (850 g.) has the following characteristics:

Coloration: yelow

Viscosity: 90 poises at 25°C.

Oh value: 17

Acid value: 9

Acrylic unsaturation: 7.5 meq./g.

EXAMPLE 9.

a. 1600 g castor oil (containing 3,0 meq. OH/g.) and 400 g maleicanhydride are introduced into the reactor described in Example 5. Themixture is agitated, heated to 125°C. and kept at that temperature for 2hours to obtain the addition product: castor oil-maleic anhydride(abbreviated as COMA) having a viscosity of 50 poises at 25°C.

b. 417 g. COMA (see above)

375 g. of the 1 mole pentaerythritol + 7 moles ethylene oxide additionproduct having a molecular weight of about 400 and sold by UGINE-KUHLMANunder the Trade Mark PLURACOL PeP 450

300 g. benzene

30 g. of a 67% aqueous solution of p-toluene-sulfonic acid, and

0.4 g. triphenyl phosphite

are introduced into the same reactor as used in a) above. The mixture isheated to boiling under nitrogen for 31/2 hours and 22 ml ofesterification water are collected, whereupon the solution is cooledunder nitrogen.

c. As soon as the temperature of the solution obtained in b) falls below50°C., 192 g. acrylic acid and 1 g. cuprous oxide are added and themixture is again boiled for 10 hours. The temperatur of the mixturereaches 105°C. at the end of the esterification and 40 ml water arecollected by distillation. The mixture is purified as in Example 5 and850 g. of the product having the following characteristics are obtained:

Viscosity at 25°C.: 200 poises

Oh value: 42

Acid value: 6.7

Acrylic unsaturation: 2.6 meq./g.

Volatile matter content: < 0.1%

EXAMPLE 10.

a. Into the reactor described in Example 5, the following areintroduced:

283 g. dimer acid (EMPOL 1038 of Emery Industries Inc., see Example 6)

73 g. adipic acid

408 g. pentaerythritol

792 g. acrylic acid

600 g. toluene

50 g. of a 67% aqueous solution of p-toluene-sulfonic acid

2 g. cuprous oxide

The mixture is boiled for 5 hours and the temperature finally reaches116°C. and 235 ml water of distillation are collected. The product ispurified as described in Example 5 and 1180 g. of a ready-for-useproduct having the following characteristics are obtained:

Viscosity at 25°C.: 125 poises

Oh value: 12

Acid value: 15

Acrylic unsaturation: 7.6 meq./g.

Volatile matter content: < 0.1%

b. If the 73 g. adipic acid of the formulation in a) above are replacedby 194 g. of1,4,5,6,7,7-hexachlorobicyclo[2.2.1]hept-5-ene-2,3-dicarboxylic acid(HET acid), a product is obtained having the following characteristics:

Viscosity at 25°C.: 440 poises

Oh value: 34

Acid value: 12

c. If the 73 g. adipic acid of the formulation in a) above are replacedby 232 g. bromophthalic acid, a product is obtained having the followingcharacteristics:

Viscosity at 25°C.: 275 poises

Oh value: 27

Acid value: 8

d. If the 73 g. adipic acid of the formulation in a) above are replacedby 83 g. isophthalic acid, a product is obtained having the followingcharacteristics:

Viscosity at 25°C.: 245 poises

Oh value: 40

Acid value: 26

EXAMPLE 11.

a. The following are introduced into the reactor described in Example 5:

102 g. adipic acid

371 g. pentaerythritol

592 g. oleic acid

529 g. acrylic acid

420 g. benzene

42 g. of a 67% aqueous solution of p-toluene-sulfonic acid

1.4 g. cuprous oxide

1.4 g. triphenyl phosphite

The mixture is boiled under nitrogen. Esterification takes 7 hours andthe temperature reaches 101°C. and 210 ml. water are collected. Theproduct is purified as in Example 5.

Viscosity at 25°C.: 12 poises

b. To 400 g. of the product prepared in a), the following are added:

18 g. of a mixture of 2,4- and 2,6-toluylene-diisocyanate

0.4 g. triethylene diamine

The mixture is heated for one hour at 65°C., whereafter 7 g. n-propanolare added and heating is continued for further 15 minutes. The thusobtained urethanized product has now a viscosity at 25°C. of 140 poises.

EXAMPLE 12.

The esterification is carried out in an enamelled metal reactor with acapacity of 150 liters, equipped with an anchor agitator and anazeotropic distillation column. The reactor is of the double-walledtype, with oil heating. The following amounts of reactants areintroduced into it:

21.47 kg. dimer acid (EMPOL 1010, see Example 7)

20.67 kg. pentaerythritol

41.04 kg. acrylic acid

20.20 kg. benzene

1.52 kg. p-toluene-sulfonic acid dissolved in 1 kg. of water

0.076 kg. cuprous oxide

0.019 kg. triphenyl phosphite

The mixture is degassed in vacuo to an absolute pressure of 150 mm. Hg.,whereupon the pressure is brought back to atmospheric pressure withnitrogen. This operation is repeated three times.

The mixture is brought to boiling temperature under reflux and the wateris eliminated. The esterification takes from 7 to 8 hours and, at thismoment, 11.47 kg. of water have been azeotropically distilled off.

The mixture is cooled and transferred to a stainless steel vessel with acapacity of 600 liters and provided with a screw agitator. The mixtureis diluted with 300 kg. of benzene and washed twice with aqueoussolutions of sodium chloride and then three times with aqueous solutionsof sodium hydrogen carbonate.

The organic solution purified in this manner is stabilized by adding 70g. hydroquinone methyl ether, the solvent then being eliminated at atemperature of 50°C. and at a pressure of 150 mm.Hg. in a thin layerevaporator until the residual solvent content is less than 0.1%.

The unsaturated resin of this Example is thus obtained with a yield ofabout 95% and it has the following characteristics:

Coloration: yellowish-brown

Viscosity: 120 poises at 25°C.

Oh value: 24

Acid value: 7

Acrylic unsaturation: 7.5 meq./g.

EXAMPLE 13.

The following materials are introduced into the apparatus described inExample 12:

22.60 kg. dimer acid (EMPOL 1010, see Example 7)

16.32 kg. pentaerythritol

30.80 kg. acrylic acid

20.00 kg. benzene

1.40 kg. p-toluene-sulfonic acid dissolved in 1 kg. water

0.080 kg. cuprous oxide

0.020 kg. triphenyl phosphite

After esterification for 8 and a half hours, 9.8 kg. of water havedistilled off.

The esterification solution is divided into two equal parts:

The first part (resin No. 13A) is purified by the technique described inExample 12.

To the second part (resin No. 13B) is added a mixture containing 3 kg.ethanol and 3 kg. benzene; the esterification is continued for 3 hours,during which time 0.950 kg. water is distilled off; this second part isthen purified by the usual technique.

The two resins thus recovered have the following characteristics:

                   Resin No. 13A                                                                           Resin No. 13B                                        ______________________________________                                        Viscosity at 25°C.                                                                      170 poises  30 poises                                        OH value          13         62                                               Acid value        8           8                                               Acrylic unsaturation (meq./g.)                                                                  6.9         5.7                                             ______________________________________                                    

Treatment by ethanol brought about transesterification, which had thefollowing consequences: reduction of the length of chains, resulting ina lowering of viscosity; producing a more homogeneous molecular weightdistribution than that of resin No. 13A, as is demonstrated bycomparison of the distribution curves of molecular mass measured bychromatography with gel permeation; increasing the OH number; andslightly reducing the acrylic unsaturation content.

EXAMPLE 14.

A resin is prepared as in Example 12 but the esterification is stoppedwhen an OH number of 48 is achieved. After purification, it has thefollowing characteristics:

Viscosity: 60 poises at 25°C.

Oh value: 48

Acid value: 9

Acrylic unsaturation: 7.5 meq./g.

1 kg. of this resin is introduced into a 2 liters double-wall glassreactor equipped with a mechanical agitator and a thermometer, and 47 g.of a mixture of 2,4-and 2.6-toluylene diisocyanate and 1 g.triethylenediamine are added thereto. The temperature is raised to60°C., while agitating, for one hour. Titration then reveals no furtherpresence of isocyanate groups. The reaction takes place in the air butthe reactor is protected against humidity by a silica gel column. Theviscosity of the mass increases progressively. The resin obtained hasthe following characteristics:

Viscosity: 395 poises at 25°C.

Oh value: 20

Acid value: 9

Acrylic unsaturation: 7.5 meq./g.

EXAMPLE 15.

a. The following mixture is esterified in the reactor described inExample 12, in the same manner as described there:

11.30 kg. dimer acid (EMPOL 1038, same as in Example 6)

10.88 kg. pentaerythritol

21.00 kg. acrylic acid

10.60 kg. benzene

1.00 kg. of a 67% aqueous solution of p-toluene-sulfonic acid 0.04 kg.cuprous oxide

0.017 kg. triphenyl phosphite

The esterification takes 5 hours. The temperature finally reaches 102°C.and 3.95 kg. water of distillation are collected.

After purification, 3.4 kg. of the product having the followingcharacteristics are obtained:

Viscosity at 25° C.: 50 poises

Oh value: 84

Acid value: 7.8

Acrylic unsaturation: 8.6 meq/g.

b. The viscosity of the product can be increased by urethanization withdifferent isocyanates. 1000 g. of the product obtained in a) hereinaboveand 0.5 g. triethylene diamine are reacted with the amounts of theisocyanates given in the following Table II. The mixture is heated to70°C. until disappearance of the isocyanate groups, which takes aboutone hour.

                                      TABLE II                                    __________________________________________________________________________    product                                                                             amount of isocyanate in g. per 1000 g.                                                                viscosity in                                                                             OH                                   No.   of product a) + 0.5 g. triethylene diamine                                                            poises at 25°C.                                                                   index                                __________________________________________________________________________    b 1   110 g. phenyl-isocyanate                                                                              210        36                                   b 2    37.3 g. toluylene-diisocyanate                                                                       195        80                                   b 3    48.8 g. hexamethylene-diisocyanate                                                                   210        55                                   b 4    46.5 g. diphenylmethane-diisocyanate                                                                 220        50                                   b 5    67.2 toluylene-diisocyanate +                                                 44.8 g. 2-hydroxyethyl acrylate                                                                      220        58                                   b 6    72.1 g. toluylene-diisocyanate +                                              30.7 g. n-butanol      215        52                                   __________________________________________________________________________

EXAMPLE 16.

A mixture of 100 parts of the resin of Example 1 and 1 part ofazobisisobutyronitrile are poured into a "Teflon"(polytetrafluorethylene) dish, the depth of which is 1 mm.

A sheet of bioriented polyethylene terephthalate with a thickness of 12micron is placed in contact with the solution in order to protect thelatter from the air. The dish is placed in a stove at 80°C. After 25minutes, hardening is complete. The polymer is insoluble in the usualsolvents. After extraction with methyl ethyl ketone in a Soxhletapparatus, a residue of 96.4% remains.

EXAMPLE 17.

The following two mixtures are prepared from the resin of Example 5:

Mixture A :

10 parts of the resin of Example 5

0.3 part of a 50% solution of benzoyl peroxide in dioctyl phthalate

0.02 part of a paraffin having a melting point of 52-54°C.

Mixture B :

10 parts of the aforesaid resin

0.3 part of a 10% solution of dimethyl-p-toluidine in butyl acrylate

0.02 part of the aforesaid paraffin.

After rapidly mixing compositions A and B, a 500 micron film is appliedto a glass plate by means of a hand coater. After a few minutes, thereaction starts at ambient temperature and the paraffin floats on thesurface. After 15 minutes, a hard, non-sticky film is obtained.

EXAMPLE 18.

A film with a thickness of 500 microns is poured on to a glass platefrom the unsaturated resin of Example 7, to which 0.5% by weight ofbenzoin methyl ether has been added.

This glass plate is placed in a tight box provided with a windowcomposed of a sheet of bioriented polyethylene terephthalate with athickness of 12 microns. Air is flushed out by passing in a current ofnitrogen for 10 minutes, followed by irradiation with a Philips HTQ-41000 Watt ultraviolet lamp placed at a distance of 25 cm.

After ultra-violet irradiation of 1 minute, the resin is perfectlyhardened (96.5% insoluble in methyl ethyl ketone).

EXAMPLE 19.

A film of the unsaturated resin of Example 8, with a thickness of 100microns, is poured on to a glass plate. This film is hardened byelectron beam curing under the following conditions:

Electron accelerator: type BBC, 300 KeV, 50 mA

Dose rate: 10 Mrad/sec.

Irradiation in an inert atmosphere obtained by flushing the surface withcombustion gases.

The film is perfectly hardened (more than 98% insoluble in methyl ethylketone) with a dose of 1 Mrad, which represents a linear speed of thefilm of 70 meters per minute.

EXAMPLE 20. FORMULATION FOR ROAD MARKING.

A paint is prepared from the following constituents:

1000 parts of the unsaturated resin of Example 13B

500 parts methyl methacrylate 370 parts ethyl acrylate 130 parts acrylicacid

4 parts paraffin, melting point 52-54°C.

2500 parts calcium carbonate, and 1000 parts titanium oxide.

From this paint, the following two compositions are prepared:

Composition A:

500 parts of the aforesaid paint

10 parts of a 50% solution of benzoyl peroxide in dioctyl phthalate

Composition B:

500 parts of the aforesaid paint

10 parts of a 10% solution of dimethyl-p-toluidine in ethyl acrylate

These two compositions are applied simultaneously and in equal amountsby means of a two-head spray gun, in bands of a thickness of 250microns, on to concrete and asphalt.

Hardening at ambient temperature is obtained in 10 minutes. Adhesion tothe two substrates is excellent. The pencil hardness is higher than 4 H.After 6 months, in the winter season, the painted surfaces are stillintact.

EXAMPLE 21. POLYVINYL CHLORIDE PLASTISOL.

A polyvinyl chloride plastisol is prepared by mixing:

100 parts of polyvinyl chloride obtained by polymerization in aqueoussuspension and having a molecular weight of 19,000

25 parts of the resin of Example 12,

4 parts of dibutyl-tin maleate,

20 parts titanium oxide,

50 parts chalk,

1 part colloidal silica (Aerosil 200, Degussa), and

1 part t-butyl hydroperoxide.

This mixture is applied to a metal sheet at a thickness of 40 micronsand heated for 10 minutes at 160°C. 100% adhesion (cross-cut), a pencilhardness of HB and an Erichsen slow penetration test value of 8 mm. areobtained.

EXAMPLE 22. ANAEROBIC ADHESIVE.

100 parts of the resin of Example 7 are mixed with 30 parts of the resinof Example 1. 2 parts cumene hydroperoxide, 0.3 parts dimethylaniline,0.2 parts benzoyl sulfimide and 0.015 part hydroquinone are added. Themixture has an initial viscosity of 22 poises; it is saturated withoxygen and kept in a thin-walled polyethylene container. During periods3 and 6 months, the viscosity increases to 25 and 32 poises,respectively.

The same product, stored in a glass container with the exclusion of air,after flushing with nitrogen, polymerizes within 5 days (viscosity >20,000 poises).

4 drops of the 22-poise mixture are applied to the threaded portion of aseries of standard 10 mm. bolts, which were then screwed by hand into alocknut. After 30 minutes, the connection cannot be unscrewed and after3 hours at 22°C. an unlocking torque of 0.64 m./kg. is measured.

EXAMPLE 23. METAL VARNISH.

An ultra-violet varnish, which can be applied to a metal sheet, isobtained by mixing:

70 parts of the unsaturated resin of Example 8

27 parts Tercarol 1 triacrylate (TERCAROL 1 is a Registered Trade Markfor the addition product of 12 moles propylene oxide on one mole ofglycerol, having a molecular weight of about 1000)

3 parts of 2-hydroxyethyl acrylate monomaleate

40 parts ethyl acrylate

5 parts diethylene glycol diacrylate

0.5 parts colloidal silica (AEROSIL 200 - Degussa)

1 part PA-520 polyethylene wax (Hoechst) and

3 parts of a mixture of benzoin butyl ether isomers (Trigonal-14;Noury-Lande).

A layer of 22 grams per square meter of the composition is applied on toa degreased tin plate sheet by means of a roller coater. The sheet ismoved at a speed of 0.5 meters per minute under an ultra-violet lamp ofthe Hanovia type, placed at right angles at a distance of 7.5 cm. fromthe sheet and having a power of 80 Watts per cm. The varnish applied inthis manner becomes hard and non-sticky (pencil hardness: 2H; 97%insoluble in methyl ethyl ketone; cross-cut adhesion test 100%).

EXAMPLE 24. PREPARATION OF AN ULTRA-VIOLET SEALER SUITABLE FORAPPLICATION TO CHIP BOARD.

A sealer of the following composition is prepared in a Werner typekneader:

40 parts of the unsaturated resin of Example 13B

0.2 part of a mixture of benzoin butyl ether isomers (Trigonal-14, seeExample 23)

5.0 parts microtalc extra

7.8 parts barium sulfate, and

47 parts calcium sulfate (Leichtspat FFF, of Harzer Gipswerke).

This composition is applied to chip boards in a layer of 150 grams persquare meter by means of a reverse roll coater.

After ultra-violet irradiation for a period of 30 seconds under aPhilips HTQ4 lamp at a distance of 25 cm., the boards have a hardsurface (Persoz hardness 120 seconds) and can be sanded.

EXAMPLE 25. VARNISH.

A varnish, which can be cured by an accelerated electron beam, isprepared from the following constituents:

70 parts of the unsaturated resin of Example 8

27 parts 1,4-butanediol diacrylate

0.5 part of colloidal silica (AEROSIL 200 - DEGUSSA), and

2.5 parts silica (SYLOID 74 made by Grace).

This varnish is applied to a glass plate in a coat of a thickness of 50microns by means of a hand coater. With a dose of 1 Mrad (irradiationconditions identical to those of Example 19), the pencil hardness isequal to 5H and the product is insoluble in methyl ethyl ketone to anextent of 96.9%.

EXAMPLE 26. PAINT

A paint which can be applied by a curtain coater and which can be curedby an accelerated electron beam is prepared from the followingconstituents:

15 parts of the unsaturated polyester described below

20 parts of the unsaturated resin of Example 13B

15 parts 1,4-butanediol acrylate

43 parts titanium oxide

4 parts Shepperd Brown 49 dye, and

3 parts silica (SYLOID 74 made by GRACE).

The unsaturated polyester used in this composition was obtained bycondensation of a mixture of maleic anhydride, adipic acid, ethyleneglycol, dipropylene glycol, and 2-ethylhexyl alcohol in a molar ratio of0.4 : 0.6 : 0.8 : 0.2 : 0.1.

This composition forms a very stable "curtain" , giving off no odour. Itis applied in coats of 120 grams per square meter on to chip boardpanels previously treated with a stopper and carefully sanded.Irradiation with an electronic beam is effected under the conditions ofExample 19. The dose necessary for perfect curing is 2 Mrad, whichrepresents a linear speed of the film of 35 meters per minute. Theappearance of the panels is excellent. The paint is glossy and very hard(Pencil hardness: 3 H), its resistance to water and solvents isexcellent and its appearance is unchanged after 500 hours exposure tothe Weather-O-matic device.

EXAMPLE 27. PAINT.

A paint which can be applied by a roller coater and cured by an electronbeam is prepared from the following constituents:

20 parts of the unsaturated resin of Example 12

12 parts of an unsaturated resin of the polyether acrylate-urethane typedescribed below

10 parts of an oligomer of the Tercarol-1 triacrylate type (described inExample 23)

12 parts 1,4-butanediol diacrylate

20 parts titanium oxide

22 parts chalk

3 parts silica (SYLOID 74), and

1 part colloidal silica (AEROSIL 200).

A coat of 52 grams per square meter is applied by a roller coater to arigid fibre board (60 × 30 cm.) previously treated with aglycerophthalic sealer.

After irradiation under the conditions described in Example 19 (2 Mrad)and at a linear speed of 35 meters per minute, a coating is obtainedwhich has a glossy finish and a pencil hardness of 4 H.

The unsaturated resin of the polyether acrylate-urethane type used inthe composition of this Example was obtained by reacting 3 moles ofpolypropylene glycol with 4 moles of isophorone diisocyanate and 2 molesof hydroxyethyl acrylate in the presence of 2% by weight (calculatedwith reference to the diisocyanate) of triethylenediamine, at 80°C. for10 hours, until the diisocyanate bands in the infra-red spectrumdisappeared.

EXAMPLE 28.

A mixture of:

68 parts of the product of Example 12

27 parts trimethylolpropane triacrylate

2 parts acrylic acid, and

3 parts benzoin ethyl ether is applied at the rate of 3 grams per squaremeter with the aid of a reverse roller coater to the face of apolyethylene film which had been treated by corona effect. A film ofaluminium is then applied to the coated face.

The laminate is passed under a Hanovia lamp (80 Watts/cm.), with thepolyethylene face turned towards the lamp, at a speed of 200 meters perminute. After ageing for 10 minutes it is no longer possible to separatethe two films without tearing the aluminium foil.

EXAMPLE 29. OFFSET INK FOR WEB PRESS.

This is prepared from the following constituents:

15 parts phthalocyanine blue (Colour Index, Pigment Blue 15)

64 parts of the unsaturated resin of Example 12

10 parts of trimethylolpropane triacrylate

5 parts dioctyl phthalate

5 parts benzoin butylether, and

1 part polyethylene wax PA-520 (HOECHST).

This ink is applied at a thickness of about 1 micron to a strip ofpaper. The latter is then passed, at variable speeds and at a distanceof 7.5 cm., under a Hanovia No. 6525 A 431 type ultra-violet lamp of62.5 cm. arc length and a power of 5000 Watts (medium pressure mercurylamp), Offsetting appears at 4 meters per second and the hardened inkbecomes unscratchable two hours after irradiation.

In four-colour printing on a rotary press equipped with three lamps ofthe type described, the ink dries at a speed of 310 meters per minute.

EXAMPLE 30. OFFSET INK FOR WEB PRESS.

An ink is prepared from the following constituents:

15 parts phthalocyanine blue (Colour Index, Pigment Blue 15)

59 parts of the unsaturated resin of Example 12

15 parts of the unsaturated resin of Example 13B

5 parts dioctyl phthalate

5 parts of a mixture of benzophenone and Michler's ketone in the weightratio 6:1, and

1 part polyethylene wax PA-520 (HOECHST).

This ink has a reactivity similar to that of Example 29.

EXAMPLE 31. OFFSET INK FOR SHEET-FED MACHINES.

An ink is prepared from the following constituents:

16 parts AAMX benzidine yellow (Colour Index, Pigment Yellow 13)

70 parts of the unsaturated resin of Example 6

4 parts trimethylolpropane triacrylate

5 parts dioctyl phthalate

4 parts 1-phenyl-1,2-propanedione 2-[O-(benzoyl)oxime], and

1 part polyethylene wax PA-520 (HOECHST).

The appearance of offsetting determined as in Example 29 occurs at 3.5-4meters per second.

In four-colour printing on a sheet-fed press equipped with threeultra-violet lamps of 80 Watts per centimeter, it was possible to workat the rate of 8,000 sheets per hour.

EXAMPLE 32. OFFSET INK FOR SHEET-FED MACHINE.

An ink is prepared from the following constituents:

16 parts AAMX benzidine yellow (Colour Index, Pigment Yellow 13)

50 parts of the unsaturated resin of Example 14

24 parts of the unsaturated resin of Example 13B

5 parts dioctyl phthalate

5 parts of a mixture of benzophenone and Michler's ketone in the weightratio 6:1, and

1 part polyethylene wax PA-520.

This ink has a reactivity similar to that of Example 31.

EXAMPLE 33.

Yellow UV-curable inks are prepared from the following constituents:

16 parts AAMX benzidine yellow (Colour Index, Pigment Yellow 13)

70 parts of one of the various binders given in Table III below

4 parts trimethylolpropane triacrylate

4 parts dioctyl phthalate

5 parts of a mixture of benzophenone and Michler's ketone in the weightratio 6:1, and

1 part polyethylene wax PA-520.

The appearance of offsetting is determined as in Example 29.

                                      TABLE III                                   __________________________________________________________________________    Formulation of the UV ink                                                                     Speed of passing under the UV lamp (m/                        with the binder of Example                                                                    second), at which offsetting appears                          __________________________________________________________________________     9              1.75                                                          10 a            3.25                                                          10 b            >4                                                            10 c            >4                                                            10 d            3.50                                                          11 b            2.5                                                           15 a            2.25                                                          15 b 1          1.75                                                          15 b 2          2.5                                                           15 b 3          3.0                                                           15 b 4          3.0                                                           15 b 5          2.75                                                          15 b 6          2.5                                                           __________________________________________________________________________

EXAMPLE 34.

In the yellow ink of Example 33 prepared with the binder of Example 15 a(non-urethanized), the 4 parts trimethylolpropane triacrylate and the 4parts dioctyl phthalate are replaced by 8 parts N-methyl-diethanolaminediacrylate.

Offsetting appears then at 3.25 m./second (gain of 1 m./second).

EXAMPLE 35. FLEXOGRAPHIC INK.

This is prepared from the following constituents:

6 parts phthalocyanine blue (Colour Index, Pigment Blue 15)

45 parts of the unsaturated resin of Example 13B

30 parts 1,4-butane-diol diacrylate

10 parts N-methyl-diethanolamine diacrylate

8 parts of a mixture of benzophenone and Michler's ketone in the weightratio 6:1, and

1 part polyethylene wax PA-520.

Offsetting, determined as in Example 29, appears at 1.75 m./second.

Application of 5 microns films is carried out with a bar-coater on thefollowing substrates

nitrocellulose varnished aluminium foil

nitrocellulose varnished Cellophane MS

polyvinylidene chloride (solution) varnished Cellophane XS₁

polyvinylidene chloride (emulsion) varnished Cellophane XS₂ polyethylenetreated by corona effect.

Drying under a UV lamp (as described in Example 29) is satisfactory atmore than 180 meters per minute. There is no offsetting between printand substrate nor any print to print sticking. The film is glossy.Adhesion, determined by the Scotch tape test, is satisfactory and theresistence to nail-scratching and rubbing are good.

EXAMPLE 36. WHITE OFF-SET INK FOR METAL DECORATION.

It has the following composition

55 parts surface-treated rutile titanium oxide

35 parts of the unsaturated resin prepared in Example 15b2

2 parts dioctyl phthalate

8 parts of a mixture of benzophenone and Michler's ketone in the weightratio 6:1.

Printing is carried out on an off-set press for tin plate decoration.Drying takes place by means of 3 medium pressure mercury vapor,air-cooled, 80 Watts per centimeter arc length, UV lamps. Speed ofprinting is 5,000 sheets per hour. The drying and adhesion propertiesallow stacking, pile stockage, handling of the iron plate stacks anduptake for the supply of presses and varnishers, which realize thesubsequent colour printing and varnishing of the tin plates.

We claim:
 1. Compounds with multiple acrylic radicals, the averagecomposition of which has the general formulaX--y-(z)_(m-p-l) ]_(n)wherein X is the radical derived by removing the OH groups from thecarboxyl groups of an organic carboxylic acid containing n COOH groupsand the number of carbon atoms of which is between 14 and 90, Y is theradical derived by removing m-p hydrogen atoms from the hydroxyl groupsof an organic compound containing m OH groups, Z is the monovalentradical derived by removing the OH group from the carboxyl group of amonocarboxylic acid having at least one terminal CH₂ =CH-COO- radical, nis a whole number from 1 to 6, m is a whole number from 2 to 8, p is anumber of from 0 to 2.5, with the proviso that m-p-l is a positivenumber different from zero and that n(m-p-l) is between 2 and
 15. 2.Compounds according to claim l, in which X is the radical derived froman organic carboxylic acid having from 18 to 54 carbon atoms, n is awhole number of from 1 to 4 and m is a whole number of from 3 to
 6. 3.Compounds according to claim 1, in which X is the radical derived froman organic aliphatic monocarboxylic acid.
 4. Compounds according toclaim 1, in which X is the radical derived from an organicpolycarboxylic acid.
 5. Compounds according to claim 1, in which X isthe radical derived from a mixture of at least 25 mole % of an organiccarboxylic acid having from 14 to 90 carbon atoms and at most 75 mole %of at least one organic aliphatic, cycloaliphatic or aromatic carboxylicacid having less than 14 carbon atoms.
 6. Compounds according to claim1, in which Y is the radical derived from an organic compound selectedfrom the group consisting of an aliphatic polyhydric alcohol, anoxyalkylated aliphatic polyhydric alcohol, a polyester-alcohol, apolyether-alcohol, an oxyalkylated polyester-alcohol and an alkoxylatedpolyether-alcohol.
 7. Compounds according to claim 1, in which Z is theradical derived from a monocarboxylic acid selected from the groupconsisting of acrylic acid, an ester of one mole of a hydroxyalkylacrylate with one mole of a dicarboxylic acid or anhydride, an ester oftwo moles of a hydroxyalkyl acrylate with one mole of a tricarboxylicacid and an ester of three moles of a hydroxylalkyl acrylate with onemole of a tetracarboxylic aicd, the alkyl radical of said hydroxyalkylacrylates having from 2 to 12 carbon atoms.
 8. A compound with multipleacrylic radicals selected from the group consisting of: the reactionproduct of 1 mole of ricinoleic acid with 1 mole of trimethylolpropaneand 3 moles of acrylic acid; the reaction product of 1 mole of stearicacid with 1 mole of sorbitol and 5 moles of the ester of 1 mole ofadipic acid with 1 mole of hydroxyethyl acrylate; the reaction productof 1 mole of oleic acid with 1 mole of dipentaerythritol and 5 moles ofthe ester of 1 mole of maleic anhydride with 1 mole of hydroxyethylacrylate; the reaction product of 1 mole of linseed oil fatty acid with1 mole of the addition product of about 12 moles of ethylene oxide with1 mole of sorbitol and 5 moles of the ester of 1 mole of phthalicanhydride with 1 mole of hydroxyethyl acrylate; the reaction product of1 mole of C₃₆ dimer acid with 2 moles of pentaerythritol and 6 moles ofacrylic acid; the reaction product of 1 mole of C₃₆ dimer acid with 2moles of the addition product of 3 moles of propylene oxide with 1 moleof glycerol and 4 moles of acrylic acid; the reaction product of 1 moleof the addition product of maleic anhydride on 9,12-linoleic acid with 3moles of ethylene glycol and 3 moles of the ester of 1 mole of maleicanhydride with 1 mole of 2-hydroxypropyl acrylate; the reaction productof 1 mole of the ester of 1 mole of pyromellitic acid and 4 moles ofricinoleic acid, with 4 moles of trimethylolpropane and 8 moles ofacrylic acid; the reaction product of 1 mole of C₃₆ dimer acid with 2moles of the addition product of 12 moles of ethylene oxide with 1 moleof glycerol and 4 moles of the ester of 1 mole of maleic anhydride with1 mole of hydroxyethyl acrylate; the reaction product of 1 mole of C₃₆dimer acid chloride with 2 moles of pentaerythritol and 6 moles ofacrylyl chloride; the reaction product of 1 mole of the addition productof maleic anhydride on 9,12-linoleic acid with 3 moles of the additionproduct of 3 moles of propylene oxide with 1 mole of glycerol and 3moles of acrylic anhydride; the reaction product of 1 mole of the dimerof methyl linoleate with 2 moles of glycerol and 4 moles of ethylacrylate; the reaction product of 1 mole of oleic acid with 1 mole ofthe addition product of 12 moles of ethylene oxide with 1 mole ofsorbitol and 5 moles of acrylic acid; the reaction product of 1 mole ofstearic acid with 1 mole of the addition product of 7 moles ethyleneoxide with 1 mole pentaerythritol and 3 moles of the ester of 1 mole ofmaleic anhydride with 1 mole of hydroxyethyl acrylate; the reactionproduct of 1 mole of the addition product of 2 moles of thioglycolicacid on 1 mole of linolenic acid with 3 moles of polyethylene glycol and3 moles of acrylic acid; the reaction product of 1 mole of the additionproduct of maleic anhydride on oleic acid with 3 moles of the additionproduct of 12 moles of ethylene oxide with 1 mole sorbitol and 15 molesof acrylic acid; the reaction product of 1 mole of the addition productof maleic anhydride on linseed oil with 2 moles of the addition productof 12 moles of ethylene oxide with 1 mole of sorbitol and 10 moles ofacrylic acid; the reaction product of 1 mole of the addition product ofmaleic anhydride on beta-eleostearic acid with 3 moles of the additionproduct of 12 moles of ethylene oxide with 1 mole of sorbitol and 15moles of acrylic acid; the reaction product of 1 mole of C₃₆ dimer acidwith 2 moles of the addition product of 12 moles of ethylene oxide with1 mole of sorbitol and 10 moles of acrylic acid; the reaction product of1 mole of the addition product of maleic anhydride on castor oil with 2moles of the addition product of 7 moles of ethylene oxide with 1 moleof pentaerythritol and 6 moles of acrylic acid; the reaction product of0.5 mole of C₃₆ dimer acid and 0.5 mole of adipic acid with 2 moles ofpentaerythritol and 6 moles of acrylic acid; the reaction product of 0.5mole of C₃₆ dimer acid and 0.5 mole of1,4,5,6,7,7-hexachlorobicyclo[2.2.1]hept-5-ene-2,3-dicarboxylic acidwith 2 moles of pentaerythritol and 6 moles of acrylic acid; thereaction product of 0.5 mole of C₃₆ dimer acid and 0.5 mole oftetrabromophthalic anhydride with 2 moles of pentaerythritol and 6 molesof acrylic acid; and the reaction product of 0.5 mole of C₃₆ dimer acidand 0.5 mole of isophthalic acid with 2 moles of pentaerythritol and 6moles of acrylic acid.
 9. A process for the preparation of compoundswith multiple acrylic radicals, the average composition of which has thegeneral formulaX--y-(z)_(m) _(-p) _(-l) m-p-l]_(n) wherein X is theradical derived by removing the OH groups from the carboxyl groups of anorganic carboxylic acid containing n COOH groups and the number ofcarbon atoms of which is between 14 and 90, Y is the radical derived byremoving m-p hydrogen atoms from the hydroxyl groups of an organiccompound containing m OH groups, Z is the monovalent radical derived byremoving the OH group from the carboxyl group of a monocarboxylic acidhaving at least one terminal CH₂ =CH-COO- radical, n is a whole numberfrom 1 to 6, m is a whole number from 2 to 8, p is a number of from 0 to2.5,with the proviso that m-p-l is a positive number different from zeroand that n(m-p-l) is between 2 and 15, which comprises reacting together1 mole of an organic carboxylic acid of the formule X(OH)_(n), n molesof an organic compound of the formula YH_(m) and n(m-l) moles of anorganic monocarboxylic acid of the formula ZOH having at least oneterminal CH₂ =CH-COO- radical, X, Y, Z, n and m having the meaningsgiven above, the reaction being carried out in the presence of anesterification catalyst, at atmospheric pressure and at a temperature offrom about 70°C. to 140°C., for a period of from 2 to 10 hours.
 10. Atwo step embodiment of the process according to claim 9, which comprisesesterifying, in a first step, the organic compound YH_(m) with theorganic carboxylic acid X(OH)_(n) and then esterifying in a second stepthe obtained hydroxy ester X-YH_(m-l))_(n) with the organicmonocarboxylic acid ZOH.
 11. A two step embodiment of the processaccording to claim 9, which comprises esterifying, in a first step, theorganic compound YH_(m) with the organic monocarboxylic acid ZOH andsubsequently esterifying in a second step the obtained hydroxy esterY(H)-Z_(m-l) with the organic carboxylic acid X(OH)_(n).
 12. A processfor decreasing the viscosity of the compounds according to claim 1,wherein said compounds are partially transesterified with an organichydroxy compound having a molecular weight lower than
 200. 13. Theprocess of claim 12, wherein the hydroxy compound is an aliphaticmonohydric alcohol, an aliphatic polyhydric alcohol or a hydroxyalkylacrylate.
 14. A process for the preparation of a polymer of thecompounds with multiple acrylic radicals according to claim 1, whichcomprises heating said compounds at a temperature of from 50°C. to250°C., in the absence of oxygen.
 15. The process of claim 14, in whichthe heating is carried out at a temperature of from 50° to 150°C. 16.The compound of claim 8 which is the reaction product of 0.5 mol of C₃₆dimer acid and 0.5 mol of adipic acid with 2 mols of pentaerythritol and6 mols of acrylic acid.